Production of Halogenoalkanes: Substitution & Addition Reactions

 Halogenoalkanes are alkanes that have one or more halogens

 They can be produced from:
o Free-radical substitution of alkanes
o Electrophilic addition of alkenes
o Substitution of an alcohol

Free-radical substitution of alkanes

 Ultraviolet light (UV) is required for the reaction to start off

 A free-radical substitution reaction is a three-step reaction consisting of initiation,
propagation and termination steps
 In the initiation step the halogen bond is broken by energy from the UV light to produce
two radicals in a homolytic fission reaction
 The propagation step refers to the progression (growing) of the substitution reaction in
a chain type reaction
 The termination step is when the chain reaction terminates (stops) due to two free
radicals reacting together and forming a single unreactive molecule
 Free-radical substitution reactions of alkanes produce halogenoalkanes

Electrophilic addition

 Halogenoalkanes can also be produced from the addition of hydrogen halides (HX)
or halogens (X2) at room temperature to alkenes
 In hydrogen halides, the hydrogen acts as the electrophile and accepts a pair of electrons
from the C-C bond in the alkene
o The major product is the one in which the halide is bonded to the most substituted
carbon atom (Markovnikov’s rule)
 In the addition of halogens to alkenes, one of the halogen atoms acts as an electrophile
and the other as a nucleophile
Electrophilic addition of hydrogen halides or hydrogen at room temperatures to alkenes
results in the formation of halogenoalkanes
Substitution of alcohols

 In the substitution of alcohols an alcohol group is replaced by a halogen to form a

halogenoalkane
 The subustition of the alcohol group for a halogen can be achieved by reacting the
alcohol with:
 HX (or KBr with H2SO4 or H3PO4 to make HX)
 PCl3 and heat
 PCl5 at room temperature
 SOCl2
Substitution of alcohols to produce halogenoalkanes
 Overview of the different ways to produce halogenoalkanes

Classifying Halogenoalkanes

 Depending on the carbon atom the halogen is attached to, halogenoalkanes can be
classified as primary, secondary and tertiary
o A primary halogenoalkane is when a halogen is attached to a carbon that itself is
attached to one other alkyl group
o A secondary halogenoalkane is when a halogen is attached to a carbon that itself
is attached to two other alkyl groups
o A tertiary halogenoalkane is when a halogen is attached to a carbon that itself is
attached to three other alkyl groups

Primary, secondary and tertiary halogenoalkanes

Nucleophilic Substitution Reactions of Halogenoalkanes

 Halogenoalkanes are much more reactive than alkanes due to the presence of
the electronegative halogens
o The halogen-carbon bond is polar causing the carbon to carry a partial positive and
the halogen a partial negative charge
 A nucleophilic substitution reaction is one in which a nucleophile attacks a carbon atom
which carries a partial positive charge
 An atom that has a partial negative charge is replaced by the nucleophile
Due to large differences in electronegativity between the carbon and halogen atom, the C-X bond
is polar

Reaction with NaOH

 The reaction of a halogenoalkane with aqueous alkali results in the formation of an alcohol
 The halogen is replaced by the OH–
 The aqueous hydroxide (OH– ion) behaves as a nucleophile by donating a pair of electrons
to the carbon atom bonded to the halogen
 Hence, this reaction is a nucleophilic substitution
o For example, bromoethane reacts with aqueous alkali when heated to form ethanol

The halogen is replaced by a nucleophile, OH–

Reaction with KCN

 The nucleophile in this reaction is the cyanide, CN– ion

 Ethanolic solution of potassium cyanide (KCN in ethanol) is heated under reflux with the
halogenoalkane
 The product is a nitrile
o For example, bromoethane reacts with ethanolic potassium cyanide when heated
under reflux to form propanenitrile
 The halogen is replaced by a cyanide group, CN–

 The nucleophilic substitution of halogenoalkanes with KCN adds an extra carbon atom to the
carbon chain
 This reaction can therefore be used by chemists to make a compound with one more carbon
atom than the best available organic starting material

Reaction with NH3

 The nucleophile in this reaction is the ammonia, NH3 molecule

 An ethanolic solution of excess ammonia (NH3 in ethanol) is heated under pressure with
the halogenoalkane
 The product is a primary amine
o For example, bromoethane reacts with excess ethanolic ammonia when heated under
pressure to form ethylamine

The halogen is replaced by an amine group, NH3

 It is very important that the ammonia is in excess as the product of the nucleophilic
substitution reaction, the ethylamine, can act as a nucleophile and attack another
bromoethane to form the secondary amine, diethylamine

Reaction with aqueous silver nitrate

 Halogenoalkanes can be broken down under reflux by water to form alcohols

o The breakdown of a substance by water is also called hydrolysis
 This reaction is classified as a nucleophilic substitution reaction with water molecules in
aqueous silver nitrate solution acting as nucleophiles, replacing the halogen in the
halogenoalkane
o For example, bromoethane reacts with aqueous silver nitrate solution to form ethanol
 The halogen is replaced by a hydroxyl group, OH–

 This reaction is similar to the nucleophilic substitution reaction of halogenoalkanes with

aqueous alkali, however, hydrolysis with water is much slower than with the OH– ion in
alkalis
o The hydroxide ion is a better nucleophile than water as it carries a full formal
negative charge
o In water, the oxygen atom only carries a partial negative charge

A hydroxide ion is a better nucleophile as it has a full formal negative charge whereas the oxygen
atom in water only carries a partial negative charge; this causes the nucleophilic substitution
reaction with water to be much slower than with aqueous alkali
  The halogenoalkanes have different rates of hydrolysis, so this reaction can be used as
a test to identify halogens in a halogenoalkane by measuring how long it takes for the test
tubes containing the halogenoalkane and aqueous silver nitrate solutions to become opaque

Halogenoalkanes: Elimination Reactions

 In an elimination reaction, an organic molecule loses a small molecule

o In the case of halogenoalkanes this small molecule is a hydrogen halide (eg. HCl)
 The halogenoalkanes are heated with ethanolic sodium hydroxide causing the C-X bond to
break heterolytically, forming an X– ion and leaving an alkene as an organic product
o For example, bromoethane reacts with ethanolic sodium hydroxide when heated to
form ethene

Hydrogen bromide is eliminated to form ethene

Exam Tip

The reaction conditions in a reaction are extremely important.

If NaOH(ethanol) is used, an elimination reaction takes place to form an alkene from a

halogenoalkane.

If NaOH(aq) is used, a nucleophilic substitution reaction takes place to form an alcohol from a
halogenoalkane.

Halogenoalkanes: SN1 & SN2 Mechanisms

 In nucleophilic substitution reactions involving halogenoalkanes, the halogen atom is

replaced by a nucleophile
 These reactions can occur in two different ways (known as SN2 and SN1 reactions) depending
on the structure of the halogenoalkane involved

SN2 reactions
  In primary halogenoalkanes, the carbon that is attached to the halogen is bonded to one
alkyl group
 These halogenoalkanes undergo nucleophilic substitution by an SN2 mechanism
o ‘S’ stands for ‘substitution’
o ‘N’ stands for ‘nucleophilic’
o ‘2’ means that the rate of the reaction (which is determined by the slowest step of the
reaction) depends on the concentration of both the halogenoalkane and the
nucleophile ions

 The SN2 mechanism is a one-step reaction

o The nucleophile donates a pair of electrons to the δ+ carbon atom to form a new bond
o At the same time, the C-X bond is breaking and the halogen (X) takes both electrons
in the bond (heterolytic fission)
o The halogen leaves the halogenoalkane as an X – ion
 For example, the nucleophilic substitution of bromoethane by hydroxide ions to form ethanol

The mechanism of nucleophilic substitution in bromoethane which is a primary halogenoalkane

SN1 reactions

 In tertiary halogenoalkanes the carbon that is attached to the halogen is bonded to three
alkyl groups
 These halogenoalkanes undergo nucleophilic substitution by an SN1 mechanism
o ‘S’ stands for ‘substitution’
o ‘N’ stands for ‘nucleophilic’
o ‘1’ means that the rate of the reaction (which is determined by the slowest step of the
reaction) depends on the concentration of only one reagent, the halogenoalkane

 The SN1 mechanism is a two-step reaction

o In the first step, the C-X bond breaks heterolytically and the halogen leaves the
halogenoalkane as an X– ion (this is the slow and rate-determining step)
o This forms a tertiary carbocation (which is a tertiary carbon atom with a positive
charge)
o In the second step, the tertiary carbocation is attacked by the nucleophile

 For example, the nucleophilic substitution of 2-bromo-2-methylpropane by hydroxide ions to

form 2-methyl-2-propanol
 The mechanism of nucleophilic substitution in 2-bromo-2-methylpropane which is a tertiary
halogenoalkane

Carbocations

 In the SN1 mechanism, a tertiary carbocation is formed

 This is not the case for SN2 mechanisms as a primary carbocation would have been formed
which is much less stable than tertiary carbocations
 This has to do with the positive inductive effect of the alkyl groups attached to the carbon
which is bonded to the halogen atom
o The alkyl groups push electron density towards the positively charged carbon,
reducing the charge density
o In tertiary carbocations, there are three alkyl groups stabilising the carbocation
whereas in primary carbocations there is only one alkyl group
o This is why tertiary carbocations are much more stable than primary ones

The diagram shows the trend in stability of primary, secondary and tertiary carbocations

 Secondary halogenoalkanes undergo a mixture of both SN1 and SN2 reactions depending on
their structure

Reactivity of Halogenoalkanes

 The halogenoalkanes have different rates of substitution reactions

 Since substitution reactions involve breaking the carbon-halogen bond
the bond energies can be used to explain their different reactivities

Halogenoalkane bond energy table

  The table above shows that the C-I bond requires the least energy to break, and is therefore
the weakest carbon-halogen bond
 During substitution reactions the C-I bond will therefore heterolytically break as follows:

R3C-I + OH– → R3C-OH + I–

halogenoalkane alcohol

 The C-F bond, on the other hand, requires the most energy to break and is, therefore,
the strongest carbon-halogen bond
 Fluoroalkanes will therefore be less likely to undergo substitution reactions

Aqueous silver nitrate

 Reacting halogenoalkanes with aqueous silver nitrate solution will result in the formation
of a precipitate
 The rate of formation of these precipitates can also be used to determine the reactivity of the
halogenoalkanes

Halogenalkane precipitates table

 The formation of the pale yellow silver iodide was the fastest (fastest nucleophilic
substitution reaction) whereas the formation of the silver fluoride was the slowest
(slowest nucleophilic substitution reaction)
 This confirms that fluoroalkanes are the least reactive and iodoalkanes are the most reactive
halogenoalkanes

The trend in reactivity of halogenoalkanes